Les matériaux composites sont utilisés dans de nombreuses structures marines et de nouvelles applications sont en cours de développement telles que les pales d’hydroliennes. La fiabilité de ces composants dans un environnement très sévère est cruciale pour la rentabilité de ces systèmes récupérateurs d’énergie des courants marins. Ces structures sont sujettes à de nombreuses forces, telles que les courants marins, les vagues, tempêtes mais également diverses agressions marines telles que l’eau de mer et la corrosion. Une compréhension approfondie du comportement au long terme de ces parties mobiles est donc essentielle. La majorité des développeurs d’hydroliennes ont préféré des pales en carbone. Ainsi il est nécessaire de comprendre comment une longue immersion dans l’océan affecte ces composites. Dans cette étude, le comportement au long terme de différents composites carbone/époxy a été étudié en utilisant des essais de vieillissement accéléré. Une diminution significative des résistances des composites a été observée après saturation en eau de mer. Pour des temps d’immersion plus longs, seulement peu de changements des propriétés apparaissent. Peu d’effets significatifs ont été observés tant sur les modules que sur la ténacité. Ces changements de propriétés sont initialement dus à la plastification de la matrice, suivis par un affaiblissement de l’interface fibre/matrice. L’endommagement peut affecter le comportement au long terme des structures composites et créer de nouveaux chemins préférentiels pour la diffusion de l’eau. En conséquence un modèle basé sur un critère couplé résistance/ténacité a été proposé pour décrire le seuil d’endommagement et basé sur un critère en ténacité pour décrire la cinétique d’endommagement. Il permet de reproduire d’une manière correcte le seuil et la cinétique d’endommagement pour des matériaux vieillis et non vieillis. L’évolution de l’entrée d’eau dans les composites a été suivie dans le but de développer un modèle de diffusion prenant en compte le nature anisotrope des composites. Ainsi le modèle de diffusion a été utilisé sur pale d’hydrolienne. Finalement des premières investigations sur le couplage entre le modèle de diffusion et l’endommagement ont été réalisées. Cette étude a contribué au développement d’outils pour quantifier la durabilité au long terme des pales d’hydroliennes en composites. / Composite materials are used in many marine structures and new applications are being developed such as tidal turbine blades. The reliability of these components, in a very severe environment, is crucial to the profitability of tidal current energy systems. These structures are subject to many forces such as ocean tides, waves, storms but also to various marine aggressions, such as sea water and corrosion. A thorough understanding of the long term behavior of the moving parts is therefore essential. The majority of tidal turbine developers have preferred carbon blades, so there is a need to understand how long immersion in the ocean affects these composites. In this study the long term behavior of different carbon/epoxy composites has been studied using accelerated ageing tests. A significant reduction of composite strengths has been observed after saturation of the material in seawater. For longer immersions only small further changes in these properties occur. No significant changes have been observed for moduli nor for composite toughness. Changes in properties are initially due to matrix plasticization, followed by reductions due to fibre/matrix interface changes. Damage can affect the long term behavior of composites structures and create new pathways for water diffusion. As a consequence a damage model has been proposed based on a coupled strength/toughness criterion to describe the threshold of damage and on a toughness criterion to describe the crack development kinetics. It describes in a correct manner the damage threshold and kinetics for the as-received material and for material after sea water ageing. The evolution of the rate of water ingress into composite materials has been followed, in order to develop a diffusion model taking into account the anisotropic nature of composites. Then the diffusion model has been applied on a tidal turbine blade. Finally a first investigation of the coupling between the diffusion model and damage has been performed. This study has contributed to the development of tools to quantify long term durability of composite tidal turbine blades.

Soy flour (SF), a by-product of the soybean oil extraction processing, was investigated for its application in soy-polypropylene composites for interior automotive applications. The emphasis of this work was the understanding of this new type of filler material and the contribution of its major constituents to its thermal stability and impact properties. For this reason, reference materials were selected to represent the protein (soy protein isolate (SPI)) and carbohydrate (soy hulls (SH)) constituents of the soy flour. Additional materials were also investigated: the residue obtained after the protein removal from the soy flour which was called insoluble soy (IS), and the remaining liquid solution after acid precipitation of the proteins, containing mostly sugars and minerals, which was called soluble sugar extract (SSE). Two treatments, potassium permanganate and autoclave, were analyzed for their potential to modify the properties of the soy composite materials. An acid treatment with sulfuric acid conducted on soy flour was also considered. The soy materials were studied by thermogravimetric analysis (TGA) under isothermal (in air) and dynamic (in nitrogen) conditions. SPI had the highest thermal stability and SSE the lowest thermal stability for the early stage of the heating process. Those two materials had the highest amount of residual mass at the end of the dynamic TGA in nitrogen. The two treatments showed minimal effect on the isothermal thermal stability of the soy materials at 200 ??C. A minor improvement was observed for the autoclave treated soy materials. Fourier transformed infrared (FTIR) spectroscopy indicated that the chemical surface composition differed according to type of the soy materials but no difference could be observed for the treatments within one type of soy material. Contact angle analysis and surface energy estimation indicated differences of the surface hydrophobicity of the soy materials according to type of material and treatment. The initial water contact angle ranged from 57 ?? for SF to 85 ?? for SH. The rate of water absorption increased dramatically after the autoclave treatment for IS and SPI. Both materials showed the highest increase in the polar surface energy fraction. In general, the major change of the surface energy was associated with change of the polar fraction. After KMnO4 treatment, the polar surface energy of SF, IS and SPI decreased while SH showed a slight increase after KMnO4 treatment. A relationship between protein content and polar surface energy was observed and seen to be more pronounced when high protein containing soy materials were treated with KMnO4 and autoclave. Based on the polar surface energy results, the most suitable soy materials for polypropylene compounding are SPI (KMnO4), SH, and IS (KMnO4) because their polar surface energy are the lowest which should make them more compatible with non-polar polymers such as polypropylene. The soy materials were compounded as 30 wt-% material loading with an injection moulding grade polypropylene blend for different combinations of soy material treatment and coupling agents. Notched Izod impact and flexural strength as well as flexural modulus estimates indicated that the mechanical properties of the autoclaved SF decreased when compared to untreated soy flour while the potassium permanganate treated SF improved in impact and flexural properties. Combinations of the two treatments and two selected (maleic anhydride grafted polypropylene) coupling agents showed improved impact and flexural properties for the autoclaved soy flour but decreased properties for the potassium permanganate treated soy flour. Scanning electron microscopy of the fractured section, obtained after impact testing of the composite material, revealed different crack propagation mechanisms for the treated SF. Autoclaved SF had a poor interface with large gaps between the material and the polypropylene matrix. After the addition of a maleic anhydride coupling agent to the autoclaved SF and polypropylene formulation, the SF was fully embedded in the polymer matrix. Potassium permanganate treated SF showed partial bonding between the material and the polymer matrix but some of the material showed poor bonding to the matrix. The acid treated SF showed cracks through the dispersed phase and completely broken components that did not bind to the polypropylene matrix. In conclusion, the two most promising soy materials in terms of impact and flexural properties improvement of soy polypropylene composites were potassium permanganate treated SF and the autoclaved SF combined with maleic anhydride coupling agent formulation.